The photocatalytic degradation of lindane (gamma-1,2,3,4,5,6-hexachlorocyclohexane) has been studied in the presence of the polyoxometalate PW(12)O(40)(3-) in aqueous solutions. Lindane is fully decomposed to CO(2), Cl(-) and H(2)O, while a great variety of intermediates has been detected using GC-MS, including aromatic compounds (dichlorophenol, trichlorophenols, tetrachlorophenol, hexachlorobenzene, di- and trichloro-benzenodiol), non-aromatic cyclic compounds (penta-, tetrachlorocyclohexene, heptachloro-cyclohexane), aliphatic compounds (tetrachloroethane) and condensation products (polychlorinated biphenyls). The number and nature of the intermediates implies that the mechanism of decomposition of lindane is based on both oxidative and reductive processes. Common intermediates have been reported during photolysis of lindane in the presence of titanium dioxide. A similar overall mechanism of poly-oxometalates and TiO(2) photocatalysis through the formation of common reactive species is suggested. (C) 2010 Elsevier B.V. All rights reserved.